Polysiloxane-containing polymers for wrinkleproofing cellulosic textiles

ABSTRACT

A process for wrinkleproofing cellulosic textiles comprises treating the textiles with a finish and drying the treated textiles, wherein the finish contains one or more water soluble or water dispersible polysiloxane-containing polymers obtainable by free radical polymerization of  
     (a) from 10 to 99% by weight of  
     (a1) from 90 to 100% by weight of singly ethylenically unsaturated monomers and  
     (a2) from 0 to 10% by weight of multiply ethylenically unsaturated monomers  
     the sum total of (a1) and (a2) being 100% by weight  
     in the presence of  
     (b) from 1 to 90% by weight of silicone derivatives containing polyalkylene oxide  
     the sum total of (a) and (b) being 100% by weight.

[0001] This invention relates to processes for wrinkleproofing cellulosic textiles, wrinkleproofing finishes, the use of the finishes and also textile treatment compositions, solid and liquid laundry detergent formulations and fabric care rinse compositions.

[0002] Cellulosic textiles are given easy care properties by treatment with condensation products of urea, glyoxal and formaldehyde, for example. The finish is applied during the manufacture of textile materials. Softening compounds are frequently further applied with the finish. Thus finished textiles are less wrinkled and creased, easier to iron and softer and smoother after laundering compared with untreated cellulose textiles.

[0003] WO 92/01773 discloses the use of microemulsified aminosiloxanes in fabric conditioners to reduce wrinkling and creasing during the laundering process. In addition, the use of aminosiloxanes is said to facilitate ironing.

[0004] WO 98/4772 discloses a process for pretreating textile materials by applying a mixture of polycarboxylic acid and a cationic softener to the textile materials. Wrinkle control is obtained as a result.

[0005] EP-A 0 300 525 discloses fabric conditioners based on crosslinkable amino-functionalized silicones that impart wrinkle control or an easy-iron effect to textiles treated therewith.

[0006] WO 99/55953 discloses fabric wrinkle control compositions. They comprise lubricants, shape retention polymers, lithium salts and optionally further ingredients such as softeners, ionic and nonionic surfactants, odor control agents and bactericides. The formulation is preferably applied to the textile material by spraying.

[0007] EP-A 0 978 556 describes a mixture of a softener and a crosslinker component having cationic properties as a fabric wrinkle and crease control composition and also a method of wrinkleproofing textiles.

[0008] WO 00/24853 describes a fabric softening formulation which provides wrinkle reducing benefits to the treated textiles. The wrinkle reducing agents used are preferably modified silicones such as aminopolydimethylsiloxane-polyalkylene oxide copolymers or sulfated or sulfonated vegetable oils such as sulfated castor oil.

[0009] It is an object of the present invention to provide a further process for wrinkleproofing cellulosic textiles and also further finishes for wrinkleproofing such textiles.

[0010] We have found that this object is achieved by a process for wrinkleproofing cellulosic textiles, which comprises treating the textiles with a finish and drying the treated textiles, wherein the finish contains one or more water soluble or water dispersible polysiloxane-containing polymers obtainable by free radical polymerization of

[0011] (a) from 10 to 99% by weight of

[0012] (a1) from 90 to 100% by weight of singly ethylenically unsaturated monomers and

[0013] (a2) from 0 to 10% by weight of multiply ethylenically unsaturated monomers

[0014] the sum total of (a1) and (a2) being 100% by weight

[0015] in the presence of

[0016] (b) from 1 to 90% by weight of silicone derivatives containing polyalkylene oxide

[0017] the sum total of (a) and (b) being 100% by weight.

[0018] The invention also provides a wrinkleproofing finish for cellulosic textiles that contains these polymers.

[0019] The polymers used according to the invention are soluble or dispersible in water. When polymerized from monomers having neutralizable radicals, their neutralized form is soluble or dispersible in water.

[0020] Useful polymerizable monomers (a) are preferably ethylenically unsaturated monomers. It is possible to polymerize a monomer alone or a combination of two or more different monomers.

[0021] The monomers can be polymerized by all customary methods of free radical polymerization. These can be for example solution polymerization, emulsion polymerization, inverse emulsion polymerization, suspension polymerization, inverse suspension polymerization or precipitation polymerization. In the case of a solution polymerization, the solvents used can be water, customary organic solvents or the silicone derivatives of the invention themselves.

[0022] The polymerization is effected in the presence of initiators which form free radicals under the polymerization conditions. Useful free radical forming initiators include all customary peroxy and azo compounds, for example peroxides, hydroperoxides and peroxy esters such as for example hydrogen peroxide, dibenzoyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, t-butyl perpivalate and t-butyl peroxy-2-ethylhexanoate, and also azo compounds, for example 2,2′-azobis(2-amidinopropane) dihydrochloride, 2,2′-azobis(2-methylbutyronitrile) and 2,2′-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride. It will be appreciated that initiator mixtures or the familiar redox initiators can also be used. The polymerization temperature is preferably in the range from 40 to 100° C. It will be appreciated that the polymerization can also be carried out outside the stated temperature range, in which case the polymerization is carried out in pressure tightly sealed apparatus at higher temperatures, for example at from 120 to 140° C. The initiators are used in the customary amounts, i.e., in amounts of for example 0.1-5 percent by weight, based on the monomers to be polymerized.

[0023] Useful ethylenically unsaturated monomers include singly unsaturated or mixtures of singly unsaturated with multiply unsaturated monomers. The C—C double bond can be mono-, di-, tri- or tetrasubstituted.

[0024] The monomers (a) of the polysiloxane-containing polymers of the present invention can comprise from 10 to 99% by weight, preferably from 50 to 95% by weight, particularly preferably from 70 to 90% by weight of all components (a) and (b).

[0025] Useful ethylenically unsaturated monomers (a1) are represented by the general formula (I):

X—C(O)CR¹═CHR²   (I)

[0026] where

[0027] X is —OH, —OM, —OR³, —NH₂, —NHR³, —N(R³)₂, where M is a cation selected from Na+, K+, Mg++, Ca++, Zn++, NH₄+, alkylammonium, dialkylammonium, trialkylammonium and tetraalkylammonium, and each R³ is independently of the other H, a linear or branched C₁-C₄₀-alkyl radical, N,N-dimethylaminoethyl, 2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, hydroxypropyl, methoxypropyl or ethoxypropyl, and

[0028] R¹ and R² are independently selected from the group consisting of H, a linear or branched C₁-C₈-alkyl radical, methoxy, ethoxy, 2-hydroxyethoxy, 2-methoxyethoxy and 2-ethoxyethyl.

[0029] Examples of useful monomers (a1) are acrylic acid and its salts, esters and amides. The acrylic acid salts can contain any desired nontoxic metal ion, unsubstituted or substituted ammonium ion as counterions.

[0030] The esters can be derived from linear or branched C₁-C₄₀- or C₃-C₄₀-alcohols or carbocyclic C₃-C₄₀-alcohols, from multiply functional alcohols having from 2 to about 8 hydroxyl groups such as ethylene glycol, hexylene glycol, glycerol and 1,2,6-hexanetriol, from aminoalcohols or from ether alcohols such as methoxyethanol, ethoxyethanol or polyethylene glycols.

[0031] It is further possible to use N,N-dialkylaminoalkyl acrylates and methacrylates and N-[dialkylamino]alkylacrylamides and -methacrylamides of the general formula (II)

[0032] where

[0033] R⁴ is H or C₁-C₈-alkyl,

[0034] R⁵ is H or methyl,

[0035] R⁶ is unsubstituted or alkyl-substituted C₁-C₂₄-alkylene,

[0036] R⁷ and R⁸ are each C₁-C₄₀-alkyl,

[0037] Z is nitrogen when x is 1 or oxygen when x is 0.

[0038] Useful monomers (a1) further include acrylic acids substituted by C₁-C₄-alkyl, CN or COOH on carbon atom 2 or 3 and also their salts, esters and amides, preferably methacrylic acid, ethacrylic acid and 3-cyanoacrylic acid. The salts, esters and amides of these substituted acrylic acids can be selected as described above for the salts, esters and amides of acrylic acid.

[0039] Useful monomers (a1) further include vinyl and allyl esters of linear or branched C₁-C₄₀- or C₃-C₄₀-carboxylic acids or carbocyclic C₃-C₄₀-carboxylic acids, such as vinyl acetate, vinyl propionate, vinyl neononanoate, vinyl neoundecanoic acid or vinyl t-butylbenzoate, vinyl or allyl halides, preferably vinyl chloride and allyl chloride, vinyl ethers, preferably methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether or dodecyl vinyl ether, vinylformamide, vinylmethylacetamide, vinylamine; vinyllactams, preferably vinylpyrrolidone and vinylcaprolactam, vinyl- and allyl-substituted heterocyclic compounds, preferably vinylpyridine, vinyloxazoline and allylpyridine.

[0040] It is further possible to use N-vinylimidazoles of the general formula III

[0041] where

[0042] R⁹ to R¹¹ are independently selected from the group consisting of H, C₁-C₄-alkyl and phenyl.

[0043] Useful monomers (a1) further include diallylamines of the general formula (IV)

[0044] where

[0045] R¹² is C₁-C₂₄-alkyl.

[0046] Useful monomers (a1) further include vinylidene chloride and unsaturated hydrocarbons such as styrene, α-methylstyrene, tert-butylstyrene, butadiene, isoprene, cyclohexadiene, ethylene, propylene, 1-butene, 2-butene, isobutylene and vinyltoluene.

[0047] Monomers having a basic nitrogen atom can be used in cationic form by neutralizing them with mineral acids, such as sulfuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid or nitric acid, or with organic acids, such as formic acid, acetic acid, lactic acid or citric acid.

[0048] Preferred monomers (a1) include acrylic acid, methacrylic acid, ethylacrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, methyl ethacrylate, ethyl ethacrylate, n-butyl ethacrylate, isobutyl ethacrylate, t-butyl ethacrylate, 2-ethylhexyl ethacrylate, decyl ethacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylates, 2-hydroxyethyl methacrylate, 2-hydroxyethyl ethacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-methoxyethyl ethacrylate, 2-ethoxyethyl methacrylate, 2-ethoxyethyl ethacrylate, hydroxypropyl methacrylate, glyceryl monoacrylate, glyceryl monomethacrylate, polyalkylene glycol (meth)acrylates and unsaturated sulfonic acids such as acrylamidopropanesulfonic acid.

[0049] Preferred monomers (a1) further include acrylamide, methacrylamide, ethacrylamide, N-methylacrylamide, N,N-dimethylacrylamide, E-ethylacrylamide, N-isopropylacrylamide, N-butylacrylamide, N-t-butylacrylamide, N-octylacrylamide, N-t-octylacrylamide, N-octadecylacrylamide, N-phenylacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-dodecylmethacrylamide, 1-vinylimidazole, 1-vinyl-2-methylimidazole, N,N-dimethylaminomethyl (meth)acrylate, N,N-diethylaminomethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate, N,N-dimethylaminobutyl (meth)acrylate, N,N-diethylaminobutyl (meth)acrylate, N,N-dimethylaminohexyl (meth)acrylate, N,N-dimethylaminooctyl (meth)acrylate, N,N-dimethylaminododecyl (meth)acrylate, N-[3-(dimethylamino)propyl]methacrylamide, N-[3-(dimethylamino)propyl]acrylamide, N-[3-(dimethylamino)butyl]methacrylamide, N-[8-(dimethylamino)octyl]methacrylamide, N-[12-(dimethylamino)dodecyl]methacrylamide and N-[3-(diethylamino)propyl]methacrylamide and N-[3-(diethylamino)propyl]acrylamide.

[0050] Preferred monomers (a1) further include maleic acid, fumaric acid, maleic anhydride and its monoesters, crotonic acid, itaconic acid, diallyldimethylammonium chloride, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether or dodecyl vinyl ether, vinylformamide, vinylmethylacetamide, vinylamine; methyl vinyl ketone, maleimide, 2-vinylpyridine, 4-vinylpyridine, 1-vinylimidazole, vinylfuran, styrene, styrenesulfonate, allyl alcohol and mixtures thereof.

[0051] Particularly preferred monomers (a1) include acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, maleic anhydride and maleic monoesters, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, acrylamide, N-t-butylacrylamide, N-octylacrylamide, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, alkylene glycol (meth)acrylate, unsaturated sulfonic acids such as for example acrylamidopropanesulfonic acid, 1-vinylpyrrolidone, 1-vinylcaprolactam, vinyl ethers (for example: methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether or dodecyl vinyl ether), vinylformamide, vinylmethylacetamide, vinylamine, 1-vinylimidazole, 1-vinyl-2-methylimidazole, N,N-dimethylaminomethyl methacrylate and N-[3-(dimethylamino)propyl]acrylamide, 3-methyl-1-vinylimidazole, diallylmethylamine, diallylethylamine, N,N-dimethylaminoethyl methacrylate and N-[3-(dimethylamino)propyl]methacrylamide.

[0052] Monomers (a1) having a quaternary nitrogen atom are particularly preferred. These are obtainable by quaternizing the aforementioned monomers having a basic nitrogen atom.

[0053] Useful quaternizing agents for the amines include for example C₁-C₂₄-alkyl halides such as methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, propyl chloride, hexyl chloride, dodecyl chloride, lauryl chloride and benzyl halides, especially benzyl chloride and benzyl bromide. Useful quaternizing agents further include dialkyl sulfates, especially dimethyl sulfate or diethyl sulfate. The basic amines can also be quaternized with alkylene oxides such as ethylene oxide or propylene oxide in the presence of acids. Preferred quaternizing agents are methyl chloride, dimethyl sulfate or diethyl sulfate.

[0054] Examples are 3-methyl-1-vinylimidazolium chloride, 3-methyl-1-vinylimidazolium methosulfate, 3-ethyl-1-vinylimidazolium ethosulfate, diallyldimethylammonium chloride, diallyldiethylammonium chloride, dimethylaminoethyl acrylate quaternized with methyl chloride, dimethyl sulfate or diethyl sulfate, dimethylaminoethyl methacrylate quaternized with methyl chloride, dimethyl sulfate or diethyl sulphate and dimethylaminopropylacrylamide quaternized with methyl chloride, dimethyl sulfate or diethyl sulfate and dimethylaminopropylmethacrylamide quaternized with methyl chloride, dimethyl sulfate or diethyl sulfate.

[0055] The quaternization can be carried out before the polymerization or after the polymerization.

[0056] Monomers (a1) having a quaternary nitrogen atom further include the reaction products of unsaturated acids, such as acrylic acid or methacrylic acid, with a quaternized epichlorohydrin of the general formula (V):

[0057] where

[0058] R¹³ is C₁-C₄₀-alkyl.

[0059] Examples are (meth)acryloyloxyhydroxypropyltrimethylammonium chloride and (meth)acryloyloxyhydroxypropyltriethylammonium chloride.

[0060] As well as the abovementioned monomers, useful monomers (a1) further include macromonomers such as for example silicone-containing macromonomers having one or more free-radically polymerizable groups or alkyloxazoline macromonomers, as described for example in EP-A 0 408 311.

[0061] It is further possible to use fluorous monomers as described for example in EP-A 0 558 423, crosslinking or molecular weight regulating compounds in combination or alone.

[0062] Useful regulators include the customary compounds known to one skilled in the art, for example sulfur compounds, (for example mercaptoethanol, 2-ethylhexyl thioglycolate, thioglycolic acid or dodecyl mercaptan), and also tribromochloromethane or other compounds having a regulating effect on the molecular weight of the polymers obtained.

[0063] It is also possible to use if desired silicone compounds containing thiol groups. Preference is given to using silicone-free regulators.

[0064] In a preferred embodiment of the invention, crosslinking doubly or more highly unsaturated monomers (a2) are used as well as singly ethylenically unsaturated monomers (a1). Generally the fraction of the doubly or more highly unsaturated monomers (a2) is from 0.05 to 10% by weight, preferably from 0.1 to 5% by weight, particularly preferably from 0.1 to 1% by weight, based on the sum total of monomers (a1) and (a2).

[0065] Monomers (a2), which have a crosslinking function, are compounds having at least two ethylenically unsaturated nonconjugated double bonds in the molecule.

[0066] Useful crosslinkers include for example acrylic esters, methacrylic esters, allyl ethers or vinyl ethers of at least dihydric alcohols. The OH groups of the parent alcohols can be wholly or partly etherified or esterified; but the crosslinkers contain at least two ethylenically unsaturated groups.

[0067] Examples of parent alcohols are dihydric alcohols, such as 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, but-2-ene-1,4-diol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,10-decanediol, 1,2-dodecanediol, 1,12-dodecanediol, neopentylglycol, 3-methylpentane-1,5-diol, 2,5-dimethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,4-bis-hydroxymethylcyclohexane, hydroxypivalic neopentylglycol monoester, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis[4-(2-hydroxypropyl)phenyl]propane, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 3-thiopentane-1,5-diol, and also polyethylene glycols, polypropylene glycols and polytetrahydrofurans having molecular weights from 200 to 10 000 in each case. As well as the homopolymers of ethylene oxide or propylene oxide it is possible to use block copolymers of ethylene oxide or propylene oxide or copolymers which contain incorporated ethylene oxide and propylene oxide groups. Examples of parent alcohols having more than two OH groups are trimethylolpropane, glycerol, pentaerythritol, 1,2,5-pentanetriol, 1,2,6-hexanetriol, triethoxycyanuric acid, sorbitan and sugars such as sucrose, glucose and mannose. It will be appreciated that the polyhydric alcohols can also be used as ethoxylates or propoxylates following reaction with ethylene oxide or propylene oxide respectively. The polyhydric alcohols may also be initially converted into the corresponding glycidyl ethers by reaction with epichlorohydrin.

[0068] Useful crosslinkers further include the vinyl esters or the esters of monohydric unsaturated alcohols with ethylenically unsaturated C₃-C₆-carboxylic acids, for example acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid. Examples of such alcohols are allyl alcohol, 1-buten-3-ol, 5-hexen-1-ol, 1-octen-3-ol, 9-decen-1-ol, dicyclopentenyl alcohol, 10-undecen-1-ol, cinnamyl alcohol, citronellol, crotyl alcohol or cis-9-octadecen-1-ol. But it is also possible to esterify the monohydric unsaturated alcohols with polybasic carboxylic acids, for example malonic acid, tartaric acid, trimellitic acid, phthalic acid, terephthalic acid, citric acid or succinic acid.

[0069] Useful crosslinkers further include esters of unsaturated carboxylic acids with the above-described polyhydric alcohols, for example of oleic acid, crotonic acid, cinnamic acid or 10-undecenoic acid.

[0070] Useful monomers (a2) further include straight-chain or branched, linear or cyclic, aliphatic or aromatic hydrocarbons having at least two olefinic double bonds which must not be conjugated in the case of aliphatic hydrocarbons, for example divinylbenzene, divinyltoluene, 1,7-octadiene, 1,9-decadiene, 4-vinyl-1-cyclo-hexene, trivinylcyclohexane or polybutadienes having molecular weights from 200 to 20 000.

[0071] Useful crosslinkers further include the acrylamides, methacrylamides and N-allylamines of at least diacid amines. Such amines are for example 1,2-diaminomethane, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,12-dodecanediamine, piperazine, diethylenetriamine or isophoronediamine. It is also possible to use the amides of allylamine and unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, or at least dibasic carboxylic acids as described above.

[0072] Useful crosslinkers further include triallylamine and triallylmonoalkylammonium salts, for example triallylmethylammonium chloride or methosulfate.

[0073] Useful crosslinkers further include N-vinyl compounds of urea derivatives, at least difunctional amides, cyanurates or urethanes, for example of urea, ethyleneurea, propyleneurea or tartramide, for example N,N′-divinylethyleneurea or N,N′-divinylpropyleneurea.

[0074] Useful crosslinkers further include divinyldioxane, tetraallylsilane or tetravinylsilane.

[0075] Preference is given to using crosslinkers which are soluble in the monomer mixture.

[0076] Particularly preferred crosslinkers include for example pentaerythrityl triallyl ether, methylenebisacrylamide, triallylamine and triallylalkylammonium salts, divinyl-imidazole, N,N′-divinylethyleneurea, reaction products of polyhydric alcohols with acrylic acid or methacrylic acid, methacrylic esters and acrylic esters of polyalkylene oxides or polyhydric alcohols which have been reacted with ethylene oxide and/or propylene oxide and/or epichlorohydrin.

[0077] Very particularly preferred crosslinkers include pentaerythrityl triallyl ether, methylenebisacrylamide, N,N′-divinylethyleneurea, triallylamine and acrylic esters of glycol, butanediol, trimethylolpropane or glycerol or acrylic esters of ethoxylated and/or chloropropoxylated glycol, butanediol, trimethylolpropane or glycerol.

[0078] The monomers (a1) and (a2), if they contain ionizable groups, can be partially or completely neutralized with acids or bases before or after the polymerization in order that the water solubility or dispersibility may be adjusted to a certain value.

[0079] Useful neutralizing agents for acid-functional monomers include for example mineral bases such as sodium carbonate, alkali metal hydroxides or ammonia, organic bases such as aminoalcohols, specifically 2-amino-2-methyl-1-propanol, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, tri[(2-hydroxy)-1-propyl]amine, 2-amino-2-methyl-1,3-propanediol and 2-amino-2-hydroxymethyl-1,3-propanediol, and also diamines such as lysine.

[0080] Useful neutralizing agents for monomers bearing basic groups include for example mineral acids such as hydrochloric acid, sulfuric acid or phosphoric acid and organic acids such as lactic acid, citric acid or others.

[0081] Useful silicone derivatives (b) include the familiar silicone surfactants of the kind available under the brandname Abil® (from T. Goldschmidt), Alkasil® (from Rhône-Poulenc), Silicone Polyol Copolymer® (from Genesee), Belsil® (from Wacker), Silwet® (from OSI) or Dow Corning® (from Dow Corning).

[0082] Particularly useful silicone derivatives (b) are those which contain the following structural elements:

[0083] where

[0084] x and y are integral numbers such that the molecular weight of the polysiloxane block is in the range from 300 to 30 000 g/mol,

[0085] R¹⁴ is at each of its instances, which can be identical or different, selected from the group consisting of the aliphatic hydrocarbon radicals of 1 to 20 carbon atoms, the cycloaliphatic hydrocarbon radicals of 3 to 20 carbon atoms and the aromatic hydrocarbon radicals of 6 to 20 carbon atoms,

[0086] where

[0087] where R¹⁷ is an organic radical of 1 to 40 carbon atoms which may contain amino, carboxylic acid or sulfonate groups,

[0088] and where

[0089] n is an integral number from 1 to 6 and a, b and c are each integral numbers from 0 to 50 with the proviso that a+b>0.

[0090] Preferred R¹⁴ groups are selected from methyl, ethyl, propyl, butyl, isobutyl, pentyl, isopentyl, hexyl, octyl, decyl, dodecyl, octadecyl, cyclohexyl, phenyl, naphthyl, benzyl, phenylethyl, tolyl and xylyl.

[0091] Preferred R¹⁵ radicals are those where the sum total of a and b is in the range from 5 to 30.

[0092] Particularly preferred —(CO)c-R¹⁷ radicals R¹⁶ are those where R¹⁷ is any desired alkyl, cycloalkyl or aryl radical of 1 to 40 carbon atoms which can be substituted by further ionogenic groups such as NH₂, COOH or SO₃H.

[0093] Particularly preferred silicone derivatives (b) are those of the general formula (VII):

[0094] where R¹⁴ is methyl, R¹⁵ is as defined above and the sum total of a+b is in the range from 5 to 30.

[0095] This invention also provides for the use of the polysiloxane-containing polymers obtainable from (a) and (b) in finishes for wrinkleproofing cellulosic textiles. Finishes are any liquid formulations which contain the polysiloxane-containing polymers in dissolved or dispersed form for application to the textile material. The finishes of the invention can be present for example as finishes in the narrower sense in the manufacture of textiles or in the form of an aqueous washing liquor or as a liquid textile treatment. Useful solvents include for example water, alcohols such as methanol, ethanol and propanol, THF or mixtures thereof. It is possible for example to treat textiles with the finish in the course of their manufacture. Textiles which have not been adequately finished, if at all, may be treated with a textile treatment that contains the polysiloxane-containing polymers for example before or after home laundering, for example during ironing. But it is also possible to treat the textiles with polysiloxane-containing polymers in the main wash cycle or after the main wash cycle in the care or softening rinse cycle of the washing machine.

[0096] The present invention also provides for the use of the polysiloxane-containing polymers obtainable from (a) and (b), in the manufacture of textiles, textile treatment before and after laundering, laundry main wash cycle, laundry conditioning rinse cycle and ironing. Different formulations are needed in each case.

[0097] The treatment before or after laundering may utilize a textile treatment composition which, as well as a polysiloxane-containing polymer in dissolved or dispersed form, contains a surfactant. In this treatment, the cellulosic textiles are for example sprayed with the polysiloxane-containing polymers with an add-on which is generally in the range from 0.01 to 10% by weight, preferably in the range from 0.1 to 7% by weight, particularly preferably in the range from 0.3 to 4% by weight, based on the weight of the dry textile material. But the finish may also be applied to the textile material by dipping the textiles into a bath which contains generally from 0.1 to 10% by weight, preferably from 0.3 to 5% by weight, based on the weight of the dry textile material, of a polysiloxane-containing polymer in dissolved or dispersed form. The textile material is either dipped only briefly into the bath or else allowed to dwell therein for a period of from 1 to 30 min for example.

[0098] Cellulosic textiles which have been treated with the finish either by spraying or by dipping are if necessary squeezed off and dried. Drying may take place in air or else in a dryer or else by subjecting the treated textile material to hot ironing. The finish becomes fixed on the textile material in the course of drying. The best conditions in each case are readily ascertainable by experimentation. The temperatures for drying, including ironing, are for example in the range from 40 to 150° C. preferably from 60 to 110° C. For ironing, the cotton program of the iron is suitable in particular. Textiles treated with the polysiloxane-containing polymers in dissolved or dispersed form according to the above-described process exhibit an excellent level of wrinkle and crease resistance that is durable to multiple laundering. There is frequently no longer any need to iron the textiles. The textiles thus treated additionally possess fiber and color protection.

[0099] The invention also provides a textile treatment composition comprising

[0100] a) from 0.1 to 40% by weight, preferably from 0.5 to 25% by weight, of at least one polysiloxane-containing polymer,

[0101] b) from 0 to 30% by weight of further silicones,

[0102] c) from 0 to 30% by weight of cationic and/or nonionic surfactants,

[0103] d) from 0 to 60% by weight of further ingredients such as further wetting agents, softeners, lubricants, water-soluble, film-forming and adhesive polymers, scents, dyes, stabilizers, fiber and color protection additives, viscosity modifiers, soil release additives, corrosion control additives, bactericides, preservatives and spraying assistants, and

[0104] e) from 0 to 99.9% by weight of water,

[0105] said components a) to e) adding up to 100% by weight.

[0106] Preferred further silicones b) are amino-containing silicones, which are preferably present in microemulsified form, alkoxylated, especially ethoxylated, silicones, polyalkylene oxide-polysiloxanes, for example the described polyalkylene oxide containing silicone derivatives used for preparing the polysiloxane-containing polymers, polyalkylene oxide-aminopolydimethylsiloxanes, silicones having quaternary ammonium groups (silicone quats) and silicone surfactants.

[0107] Useful softeners or lubricants include for example oxidized polyethylenes or paraffinic waxes and oils. Useful water-soluble, film-forming and adhesive polymers include for example (co)polymers based on acrylamide, N-vinylpyrrolidone, vinylformamide, N-vinylimidazole, vinylamine, N,N′-dialkylaminoalkyl (meth)acrylates, N,N′-dialkylaminoalkyl(meth)acrylamides, (meth)acrylic acid, alkyl (meth)acrylates and/or vinylsulfonate. The aforementioned basic monomers may also be used in quaternized form.

[0108] A pretreatment formulation to be applied to the textile material by spraying may additionally include a spraying assistant. In some cases, it can also be of advantage to include in the formulation alcohols such as ethanol, isopropanol, ethylene glycol or propylene glycol. Further customary additives are scents, dyes, stabilizers, fiber and color protection additives, viscosity modifiers, soil release additives, corrosion control additives, bactericides and preservatives in customary amounts.

[0109] The textile treatment composition may generally also be applied by spraying in the course of ironing after laundering. This not only substantially facilitates the ironing, but also imparts sustained wrinkle and crease resistance to the textiles.

[0110] The polysiloxane-containing polymers may also be used when the textiles are washed in the main wash cycle of the washing machine.

[0111] The invention further provides a solid laundry detergent formulation containing

[0112] a) from 0.05 to 20% by weight of at least one polysiloxane polymer,

[0113] b) from 0 to 20% by weight of further silicones,

[0114] c) from 0.1 to 40% by weight of at least one nonionic and/or anionic surfactant,

[0115] d) from 0 to 50% by weight of inorganic builders,

[0116] e) from 0 to 10% by weight of organic cobuilders,

[0117] f) from 0 to 60% by weight of further customary ingredients such as standardizers, enzymes, perfumes, complexing agents, corrosion inhibitors, bleaches, bleach activators, bleach catalysts, cationic surfactants, dye transfer inhibitors, soil antiredeposition agents, soil release additives, dyes, bactericides, dissolution improvers and/or disintegrants,

[0118] said components a) to f) adding up to 100% by weight.

[0119] A solid laundry detergent formulation according to the invention is customarily present in powder or granule form or in extrudate or tablet form.

[0120] The present invention further provides a liquid laundry detergent formulation containing

[0121] a) from 0.05 to 20% by weight of at least one siloxane-containing polymer,

[0122] b) from 0 to 20% by weight of further silicones,

[0123] c) from 0.1 to 40% by weight of at least one nonionic and/or anionic surfactant,

[0124] d) from 0 to 20% by weight of inorganic builders,

[0125] e) from 0 to 10% by weight of an organic cobuilder,

[0126] f) from 0 to 60% by weight of further customary ingredients such as sodium carbonate, enzymes, perfume, complexing agents, corrosion inhibitors, bleaches, bleach activators, bleach catalysts, cationic surfactants, dye transfer inhibitors, soil antiredeposition agents, soil release additives, dyes, bactericides, nonaqueous solvents, solubilizers, hydrotropes, thickeners and/or alkanolamines,

[0127] g) from 0 to 99.85% by weight of water,

[0128] said components a) to g) adding up to 100% by weight.

[0129] Useful silicones b) include the abovementioned silicones.

[0130] Useful anionic surfactants c) are in particular:

[0131] (fatty) alcohol sulfates of (fatty) alcohols having from 8 to 22, preferably from 10 to 18, carbon atoms, for example C₉- to C₁₁-alcohol sulfates, C₁₂- to C₁₄-alcohol sulfates, C₁₂- to C₁₈-alcohol sulfates, lauryl sulfate, cetyl sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate and tallow fatty alcohol sulfate;

[0132] sulfated alkoxylated C₈- to C₂₂-alcohols (alkyl ether sulfates). Compounds of this kind are prepared for example by first alkoxylating a C₈- to C₂₂-alcohol, preferably a C₁₀- to C₁₈-alcohol, for example a fatty alcohol, and then sulfating the alkoxylation product. The alkoxylation is preferably carried out using ethylene oxide;

[0133] linear C₈- to C₂₀-alkylbenzenesulfonates (LAS), preferably linear C₉- to C₁₃-alkylbenzenesulfonates and -alkyltoluenesulfonates;

[0134] alkanesulfonates such as C₈- to C₂₄-alkanesulfonates, preferably C₁₀- to C₁₈-alkanesulfonates;

[0135] soaps such as, for example, the sodium and potassium salts of C₈- to C₂₄-carboxylic acids.

[0136] The anionic surfactants mentioned are preferably included in the laundry detergent in the form of salts. Suitable cations in these salts are alkali metal ions such as sodium, potassium and lithium and ammonium ions such as hydroxyethylammonium, di(hydroxyethyl)ammonium and tri(hydroxyethyl)ammonium.

[0137] Useful nonionic surfactants c) are in particular:

[0138] alkoxylated C₈- to C₂₂-alcohols such as fatty alcohol alkoxylates or oxo alcohol alkoxylates. These may have been alkoxylated with ethylene oxide, propylene oxide and/or butylene oxide. Useful surfactants here include all alkoxylated alcohols which contain at least two molecules of one of the aforementioned alkylene oxides. Here it is possible to use block polymers of ethylene oxide, propylene oxide and/or butylene oxide or addition products which contain the aforementioned alkylene oxides in random distribution. Nonionic surfactants generally contain from 2 to 50, preferably from 3 to 20, mol of at least one alkylene oxide per mole of alcohol. The alkylene oxide component is preferably ethylene oxide. The alcohols preferably have from 10 to 18 carbon atoms. Depending on the type of alkoxylation catalyst used to make them, alkoxylates have a broad or narrow alkylene oxide homolog distribution;

[0139] alkylphenol alkoxylates such as alkylphenol ethoxylates having C₆- to C₁₄-alkyl chains and from 5 to 30 alkylene oxide units;

[0140] alkylpolyglucosides having from 8 to 22, preferably from 10 to 18, carbon atoms in the alkyl chain and generally from 1 to 20, preferably from 1.1 to 5, glucoside units;

[0141] N-alkylglucamides, fatty acid amide alkoxylates, fatty acid alkanolamide alkoxylates and also block copolymers of ethylene oxide, propylene oxide and/or butylene oxide.

[0142] Useful inorganic builders d) are in particular:

[0143] crystalline or amorphous aluminosilicates having ion-exchanging properties such as zeolites in particular. Useful zeolites include in particular zeolites A, X, B, P, MAP and HS in their sodium form or in forms in which sodium has been partly replaced by other cations such as lithium, potassium, calcium, magnesium or ammonium;

[0144] crystalline silicates such as in particular disilicates or sheet-silicates, for example δ-Na₂Si₂O₅ or β-Na₂Si₂O₅. Silicates can be used in the form of their alkali metal, alkaline earth metal or ammonium salts, preferably as sodium, lithium and magnesium silicates;

[0145] amorphous silicates such as for example sodium metasilicate or amorphous disilicate;

[0146] carbonates and bicarbonates. These can be used in the form of their alkali metal, alkaline earth metal or ammonium salts. Preference is given to sodium, lithium and magnesium carbonates or bicarbonates, especially sodium carbonate and/or sodium bicarbonate;

[0147] polyphosphates such as for example pentasodium triphosphate.

[0148] Useful organic cobuilders e) include in particular low molecular weight, oligomeric or polymeric carboxylic acids.

[0149] Useful low molecular weight carboxylic acids include for example citric acid, hydrophobic modified citric acid such as for example agaric acid, malic acid, tartaric acid, gluconic acid, glutaric acid, succinic acid, imidodisuccinic acid, oxydisuccinic acid, propanetricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid, alkyl- and alkenylsuccinic acids and aminopolycarboxylic acids such as for example nitrilotriacetic acid, β-alaninediacetic acid, ethylenediaminetetraacetic acid, serinediacetic acid, isoserinediacetic acid, N-(2-hydroxyethyl)iminodiacetic acid, ethylenediaminedisuccinic acid and methyl- and ethylglycinediacetic acid;

[0150] useful oligomeric or polymeric carboxylic acids include for example homopolymers of acrylic acid, oligomaleic acids, copolymers of maleic acid with acrylic acid, methacrylic acid, C₂-C₂₂-olefins such as for example isobutene or long-chain α-olefins, vinyl alkyl ethers having C₁-C₈-alkyl groups, vinyl acetate, vinyl propionate, (meth)acrylic esters of C₁- to C₈-alcohols and styrene. Preference is given to using the homopolymers of acrylic acid and copolymers of acrylic acid with maleic acid. Polyaspartic acids are also useful as organic cobuilders. Oligomeric and polymeric carboxylic acids are used in acid form or as sodium salt.

[0151] Useful bleaches include for example adducts of hydrogen peroxide with inorganic salts such as for example sodium perborate monohydrate, sodium perborate tetrahydrate or sodium carbonate perhydrate or percarboxylic acids such as for example phthalimidopercaproic acid.

[0152] Useful bleach activators include for example N,N,N′,N′-tetraacetylethylenediamine (TAED), sodium p-nonanoyloxybenzenesulfonate or N-methylmorpholinium acetonitrile methosulfate.

[0153] Preferred enzymes for use in laundry detergents are proteases, lipases, amylases, cellulases, oxidases or peroxidases.

[0154] Useful dye transfer inhibitors include for example homo- and copolymers of 1-vinylpyrrolidone, of 1-vinylimidazole or of 4-vinylpyridine N-oxide. Useful dye transfer inhibitors further include homo- and copolymers of 4-vinylpyridine which have been reacted with chloroacetic acid.

[0155] A detailed description of the laundry detergent ingredients mentioned is found for example in WO 99/06524 or WO 99/04313 and in Liquid Detergents, Editor: Kuo-Yann Lai, Surfactant Sci. Ser., Vol. 67, Marcel Decker, New York, 1997, p. 272-304.

[0156] The concentration of the polysiloxane-containing polymers in the wash liquor is for example in the range from 10 to 5 000 ppm, preferably in the range from 50 to 1 000 ppm. Textiles treated with the polysiloxane-containing polymers in the main wash cycle of the washing machine not only wrinkle substantially less than untreated textiles, they are also easier to iron, softer and smoother, more dimensionally and shape stable and, because of their fiber and color protection, look less used, i.e., exhibit less fluff and fewer knots and less color damage or fading, after repeated washing.

[0157] The polysiloxane-containing polymers may be used in the softening or care rinse cycle following the main wash cycle. The concentration of the polysiloxane-containing polymers in the wash liquor is for example in the range from 10 to 5 000 ppm, preferably in the range from 50 to 1 000 ppm. The rinse liquor may if desired include ingredients typical for a fabric conditioner or refresher. Textiles treated in this way and then dried on the line or preferably in a tumble dryer likewise exhibit a very high level of crease resistance that is associated with the positive effects on ironing that were described above. Crease resistance can be substantially enhanced by briefly ironing the textiles once after drying. The treatment in the softening or care rinse cycle also has a favorable effect on the shape retention of the textiles. It further inhibits the formation of knots and fluff and suppresses color damage.

[0158] The invention further provides a fabric care rinse composition containing

[0159] a) from 0.05 to 40% by weight of at least one polysiloxane polymer,

[0160] b) from 0 to 20% by weight of further silicones,

[0161] c) from 0.1 to 40% by weight of at least one cationic surfactant,

[0162] d) from 0 to 30% by weight of nonionic surfactants,

[0163] e) from 0 to 30% by weight of other customary ingredients such as lubricants, wetting agents, film forming polymers, scents, dyes, stabilizers, fiber and color protection additives, viscosity modifiers, soil release additives, corrosion control additives, bactericides and preservatives, and

[0164] f) from 0 to 99.85% by weight of water.

[0165] said components a) to f) adding up to 100% by weight.

[0166] Useful further silicones b) include the abovementioned silicones.

[0167] Preferred cationic surfactants b) are selected from the group of the quaternary diesterammonium salts, the quaternary tetraalkylammonium salts, the quaternary diamidoammonium salts, the amidoamine esters and imidazolium salts. These are preferably present in an amount of from 3 to 30% by weight in the fabric care rinse compositions. Examples are quaternary diesterammonium salts which have two C₁₁- to C₂₂-alk(en)ylcarbonyloxy(mono- to pentamethylene) radicals and two C₁- to C₃-alkyl or -hydroxyalkyl radicals on the quaternary nitrogen atom and, for example, chloride, bromide, methosulfate or sulfate as counterion.

[0168] Quaternary diesterammonium salts further include in particular those which have a C₁₁- to C₂₂-alk(en)ylcarbonyloxytrimethylene radical bearing a C₁₁- to C₂₂-alk(en)ylcarbonyloxy radical on the central carbon atom of the trimethylene group and three C₁- to C₃-alkyl or -hydroxyalkyl radicals on the quaternary nitrogen atom and, for example, chloride, bromide, methosulfate or sulfate as counterion.

[0169] Quaternary tetraalkylammonium salts are in particular those which have two C₁- to C₆-alkyl radicals and two C₈- to C₂₄-alk(en)yl radicals on the quaternary nitrogen atom and, for example, chloride, bromide, methosulfate or sulfate as counterion.

[0170] Quaternary diamidoammonium salts are in particular those which bear two C₈- to C₂₄-alk(en)ylcarbonylaminoethylene radicals, a substituent selected from hydrogen, methyl, ethyl and polyoxyethylene having up to 5 oxyethylene units and as fourth radical a methyl group on the quaternary nitrogen atom and, for example, chloride, bromide, methosulfate or sulfate as counterion.

[0171] Amidoamino esters are in particular tertiary amines bearing a C₁₁- to C₂₂-alk(en)ylcarbonylamino(mono- to trimethylene) radical, a C₁₁- to C₂₂-alk(en)ylcarbonyloxy(mono- to trimethylene) radical and a methyl group as substituents on the nitrogen atom.

[0172] Imidazolinium salts are in particular those which bear a C₁₄- to C₁₈-alk(en)yl radical in position 2 of the heterocycle, a C₁₄- to C₁₈-alk(en)ylcarbonyl(oxy or amino)ethylene radical on the neutral nitrogen atom and hydrogen, methyl or ethyl on the nitrogen atom carrying the positive charge, while counterions here are for example chloride, bromide, methosulfate or sulfate.

[0173] The examples hereinbelow illustrate the invention.

EXAMPLES

[0174] The percentages in the examples are by weight, unless the context suggests otherwise.

[0175] The K values are determined after H. Fikentscher, Cellulose Chemie, volume 13, pages 58 to 64 and 71 to 74 (1932).

[0176] The Wacker Belsil® DMC 6031 and 6032 silicone surfactants used in the examples are available from Wacker Chemie GmbH, Munich, and have the following general structure:

[0177] where R=H, —CO—CH₃.

[0178] The Silwet® 7602 and 7604 silicone surfactants are obtainable from Witco Corporation, Greenwich, Conn., USA and have the following general structure:

[0179] The Dow Corning 190 silicone surfactants are available from Dow Corporation, Midland, Mich., USA.

[0180] Further silicone derivatives (b) are preparable by methods known to one skilled in the art as described for example in EP 775 717.

General Method for Synthesis Examples A to H

[0181] The initial charge and 4.7 g of feed 2 were heated to 60° C. in a nitrogen-purged stirred apparatus. Feed 1 and the rest of feed 2 were then added dropwise over 3 hours. This was followed by a further hour of stirring to complete the polymerization. The mixture was then heated to 70° C., and feed 3 was added dropwise over 15 minutes. The mixture was stirred for a further 3 h. This provided a clear yellowish polymer solution. The mixture was adjusted to the desired solids content with feed 4.

Example A

[0182] Polymerization of 1-vinylpyrrolidone and diallyldimethylammonium chloride (in a mass ratio of 80:20) in the presence of 10% by weight of Belsil® DMC 6031 (based on total amount of monomers) and 0.3% by weight of triallylamine (based on total amount of monomers) Initial charge: 24 g of vinylpyrrolidone, 9.2 g of diallyldimethylammonium chloride (65% by weight in water), 30 g of Wacker Belsil 6031, in 200 g of water, adjusted to pH 6.5 with H₂SO₄ Feed 1: 190 g of vinylpyrrolidone, 83.1 g of diallyldimethylammonium chloride (65% by weight in water), 0.9 g of triallylamine, in 300 g of water, adjusted to pH 6.5 with H₂SO₄ Feed 2: 3.0 g of 2,2′-azobis(2-amidinopropane) dihydrochloride in 97 g of H₂O Feed 3: 1.0 g of 2,2′-azobis(2-amidinopropane) dihydrochloride in 5 g of water Feed 4: 500 g of water Polymer solids content 24% by weight properties: K value 73 (0.5% by weight in 0.5 M NaCl)

Example B

[0183] Polymerization of 1-vinylpyrrolidone and diallyldimethylammonium chloride (in a mass ratio of 70:30) in the presence of 20% by weight of Belsil® DMC 6031 (based on total amount of monomers) and 0.8% by weight of triallylamine (based on total amount of monomers) Initial charge: 18.9 g of vinylpyrrolidone, 12.5 g of diallyldimethylammonium chloride (65% by weight in water), 65 g of Wacker Belsil 6031, in 200 g of water, adjusted to pH 6.5 with H₂SO₄ Feed 1: 160 g of vinylpyrrolidone, 135 g of diallyldimethylammonium chloride (65% by weight in water), 2.7 g of triallylamine, in 300 g of water, adjusted to pH 6.5 with H₂SO₄ Feed 2: 2.7 g of 2,2′-azobis(2-amidinopropane) dihydrochloride in 97 g of H₂O Feed 3: 2.7 g of 2,2′-azobis(2-amidinopropane) dihydrochloride in 5 g of water Feed 4: 400 g of water Polymer solids content 21.8% by weight properties: K value 65.7 (0.5% by weight in 0.5 M NaCl)

Example C

[0184] Polymerization of 1-vinylpyrrolidone and 3-methyl-1-vinylimidazolium methosulfate (in a mass ratio of 80:20) in the presence of 10% by weight of Belsil® DMC 6031 (based on total amount of monomers) and 0.2% by weight of triallylamine (based on total amount of monomers) Initial charge: 17.3 g of vinylpyrrolidone, 10 g of 3-methyl-1- vinylimidazolium methosulfate solution (45% by weight in water), 35 g of Wacker Belsil 6031, in 200 g of water, adjusted to pH 6.5 with NaOH Feed 1: 190 g of vinylpyrrolidone, 120 g of 3-methyl-1- vinylimidazolium methosulfate solution (45% by weight in water), 0.6 g of triallylamine, in 300 g of water, adjusted to pH 6.5 with NaOH Feed 2: 2.7 g of 2,2′-azobis(2-amidinopropane) dihydrochloride in 97 g of H₂O Feed 3: 1.35 g of 2,2′-azobis(2-amidinopropane) dihydrochloride in 5 g of water Feed 4: 400 g of water Polymer solids content 21.5% by weight properties: K value 81.5 (0.5% by weight in 0.5 M NaCl)

Example D

[0185] Polymerization of 1-vinylpyrrolidone and diallyldimethylammonium chloride (in a mass ratio of 80:20) in the presence of 10% by weight of Silwet L 7604 (based on total amount of monomers) and 0.3% by weight of triallylamine (based on total amount of monomers) Initial charge: 21.6 g of vinylpyrrolidone, 8.3 g of diallyldimethylammonium chloride (65% by weight in water), 30 g Silwet L 7604, in 200 g of water, adjusted to pH 6.5 with NaOH Feed 1: 194.4 g of vinylpyrrolidone, 80 g of diallyldimethylammonium chloride, 0.9 g of triallylamine, 300 g of water, adjusted to pH 6.5 with H₂SO₄ Feed 2: 2.7 g of 2,2′-azobis(2-amidinopropane) dihydrochloride in 97 g of H₂O Feed 3: 2.7 g of 2,2′-azobis(2-amidinopropane) dihydrochloride in 97 g of water Feed 4: 400 g of water Polymer solids content 22.6% by weight properties: K value 58.7 (0.5% by weight in 0.5 M NaCl)

Example E

[0186] Polymerization of 1-vinylpyrrolidone, acrylamide and N-ethyl-N,N-dimethylammonium methyl methacrylate ethosulfate (in a mass ratio of 42:38:20) in the presence of 10% by weight of Belsil® DMC 6031 (based on total amount of monomers) and 0.2% by weight of triallylamine (based on total amount of monomers) Initial charge: 7.4 g of vinylpyrrolidone, 6.7 g of acrylamide, 8.2 g of N-ethyl-N,N-dimethylammonium ethyl methacrylate ethosulfate (50% by weight in water), 25 g of Wacker Belsil 6031, in 200 g of water, adjusted to pH 6.5 with NaOH Feed 1: 100 g of vinylpyrrolidone, 90 g of acrylamide, 97.2 g of N-ethyl-N,N-dimethylammonium ethyl methacrylate ethosulfate (50% by weight in water), 0.54 g of triallylamine, in 300 g of water, adjusted to pH 6.5 with NaOH Feed 2: 2.7 g of 2,2′-azobis(2-amidinopropane) dihydrochloride in 97 g of H₂O Feed 3: 1.35 g of 2,2′-azobis(2-amidinopropane) dihydrochloride in 5 g of water Feed 4: 750 g of water Polymer solids content 22.8% by weight properties: K value 85 (0.5% by weight in 0.5 M NaCl)

Example F

[0187] Polymerization of 1-vinylpyrrolidone and 3-methyl-1-vinylimidazolium methosulfate (in a mass ratio of 90:10) in the presence of 10% by weight of Belsil® DMC 6032 (based on total amount of monomers) and 0.2% by weight of triallylamine (based on total amount of monomers) Initial charge: 24.3 g of vinylpyrrolidone, 6 g of 3-methyl-1- vinylimidazolium methosulfate solution (45% by weight in water), 30 g of Wacker Belsil 6031, in 200 g of water, adjusted to pH 6.5 with NaOH Feed 1: 218 g of vinylpyrrolidone, 54 g of 3-methyl-1- vinylimidazolium methosulfate (45% by weight in water), 0.54 g of triallylamine, in 300 g of water, adjusted to pH 6.5 with NaOH Feed 2: 2.7 g of 2,2′-azobis(2-amidinopropane) dihydrochloride in 97 g of H₂O Feed 3: 1.35 g of 2,2′-azobis(2-amidinopropane) dihydrochloride in 5 g of water Feed 4: 400 g of water Polymer solids content 20.4% by weight properties: K value 82.8 (0.5% by weight in 0.5 M NaCl)

Example G

[0188] Polymerization of acrylamide and 3-methyl-1-vinylimidazolium methosulfate (in a mass ratio of 80:20) in the presence of 10% by weight of Silwet L7602 (based on total amount of monomers) and 0.2% by weight of triallylamine (based on total amount of monomers) Initial charge: 36 g of acrylamide, 18 g of 3-methyl-1- vinylimidazolium methosulfate (45% by weight in water), 42 g of Silwet L7602, in 300 g of water, adjusted to pH 6.5 with NaOH Feed 1: 298 g of acrylamide, 162 g of 3-methyl-1- vinylimidazolium methosulfate (45% by weight in water), in 450 g of water, adjusted to pH 6.5 with NaOH Feed 2: 4 g of 2,2′-azobis(2-amidinopropane) dihydrochloride in 97 g of H₂O Feed 3: 2 g of 2,2′-azobis(2-amidinopropane) dihydrochloride in 5 g of water Feed 4: 600 g of water Polymer solids content 21.5% by weight properties: K value 60 (0.5% by weight in 0.5 M NaCl)

Example H

[0189] Polymerization of 1-vinylpyrrolidone and N-ethyl-N,N-dimethylammonium propylmethacrylamide ethosulfate (in a mass ratio of 80:20) in the presence of 10% by weight of Silwet L7604 (based on total amount of monomers) Initial charge: 24 g of vinylpyrrolidone, 10 g of N-ethyl-N,N- dimethylammonium propylmethacrylamide ethosulfate (50% by weight in water), 27.5 g of Silwet L7604 in 200 g of water, adjusted to pH 6.5 with NaOH Feed 1: 200 g of vinylpyrrolidone, 100 g of N-ethyl-N,N- dimethylammonium propylmethacrylamide ethosulfate (50% by weight in water), in 300 g of water, adjusted to pH 6.5 with NaOH Feed 2: 4.0 g of 2,2′-azobis(2-amidinopropane) dihydrochloride in 97 g of H₂O Feed 3: 1.35 g of 2,2′-azobis(2-amidinopropane) dihydrochloride in 5 g of water Feed 4: 400 g of water Polymer solids content 21.5% by weight properties: K value 38 (0.5% by weight in 0.5 M NaCl)

General Method for Synthesis Examples I and J

[0190] In a nitrogen-purged stirred apparatus, the initial charge was heated to 75° C. and feeds 1 and 2 were then metered in over 3 hours. To lower the viscosity of the polymer melt, 100 g of feed 3 were added. The reaction mixture was stirred at 75° C. for a further hour. Addition of feed 4 was followed by supplementary polymerization at 75° C. for 2 hours. A steam distillation was carried out to exchange the solvent. The desired solids content was set with feed 3. This provided a yellowish viscous polymer solution.

Example I

[0191] Polymerization of 1-vinylpyrrolidone, N-ethyl-N,N-dimethylammonium propylmethacrylamide ethosulfate and tert-butyl methacrylate (in mass ratio of 70:30:10) in the presence of 10% by weight of Belsil DMC 6031 (based on total amount of monomers) Initial charge: 50 g of Belsil DMC 6031 Feed 1: 350 g of 1-vinylpyrrolidone, 200 g of N-ethyl-N,N- dimethylammonium propylmethacrylamide ethosulfate (50% by weight in water), 50 g of tert-butyl methacrylate Feed 2: 5 g of tert-butyl perpivalate (75% by weight), 60 g of isopropanol Feed 3: 600 g of DM water Feed 4: 1.5 g of tert-butyl perpivalate (75% by weight), 5 g of isopropanol Polymer Solids content 25.5% by weight properties: K value 70 (0.5% by weight in 0.5 M NaCl)

Example J

[0192] Polymerization of 1-vinylpyrrolidone, N-vinylcaprolactam and 3-methyl-1-vinylimidazolium methosulfate (in mass ratio of 60:20:20) in the presence of 10% by weight of Belsil DMC 6032 (based on total amount of monomers) Initial charge: 50 g of Belsil DMC 6032 Feed 1: 300 g of 1-vinylpyrrolidone, 100 g of N- vinylcaprolactam and 222.2 g of 3-methyl-1- vinylimidazolium methosulfate (45% by weight in water) Feed 2: 4 g of tert-butyl perpivalate (75% by weight), 50 g of isopropanol Feed 3: 600 g of DM water Feed 4: 1.3 g of tert-butyl perpivalate (75% by weight), 5 g of isopropanol Polymer solids content 23.2% by weight properties: K value 85 (0.5% by weight in 0.5 M NaCl)

Finishing of Fabric Samples

[0193] The finish used was a 1% by weight solution of the polymers according to examples A to J.

[0194] Cotton fabrics having the size reported in Table 1 and the basis weight of 160 g/m2 were sprayed on both sides with the finishes as per examples A-J in such a way that the add-on was 2%, based on the particular weight of the dry textile material, and then hot pressed while still slightly moist.

[0195] The fabric samples thus treated and, for comparison, untreated fabric samples of the same size were washed in the presence of ballast fabric with a liquid laundry detergent at 40° C. in an automatic domestic washing machine (load in the range from 1.5 to 3.0 kg) and then tumble-dried. A standard washing program and a standard drying program (respectively 40° C. colored wash and the cupboard dry program) were used. After drying, the sheetlike fabric samples were visually rated on the lines of AATCC test method 124, where a rating of 1 indicates that the fabric is highly wrinkled and has many creases and the rating of 5 is awarded to wrinkle- and crease-free fabric. The fabric samples pretreated with the finishes A, B and C received ratings between 2 and 3.5. In contrast, the untreated fabric samples each received a rating of 1. TABLE 1 Cotton Cotton Cotton (40 cm × 40 cm) (40 cm × 40 cm) (40 cm × 80 cm) Load 1.5 kg Load 3.0 kg Load 1.5 kg Untreated 1 1 1 A 3.5 3 3.5 B 3 2.5 3 C 3 3 2.5 D 3.5 3 3.5 E 3 2 2.5 F 3.5 2.5 2.5 G 3 3 3 H 3 2 2.5 I 2.5 2 2 J 3 2.5 2.5 

We claim:
 1. A process for wrinkleproofing cellulosic textiles, which comprises treating the textiles with a finish and drying the treated textiles, wherein the finish contains one or more water soluble or water dispersible polysiloxane-containing polymers obtainable by free radical polymerization of (a) from 10 to 99% by weight of (a1) from 90 to 100% by weight of singly ethylenically unsaturated monomers and (a2) from 0 to 10% by weight of multiply ethylenically unsaturated monomers the sum total of (a1) and (a2) being 100% by weight in the presence of (b) from 1 to 90% by weight of silicone derivatives containing polyalkylene oxide the sum total of (a) and (b) being 100% by weight.
 2. The use of polysiloxane-containing polymers as defined in claim 1 in textile treatment compositions, solid and liquid laundry detergent formulations and fabric care rinse compositions.
 3. The use of finishes containing polysiloxane-containing polymers as defined in claim 1 in the manufacture of textiles, textile treatment, laundry main wash cycle, laundry conditioning rinse cycle and ironing.
 4. A finish for wrinkleproofing cellulosic textiles, containing polysiloxane-containing polymers as defined in claim
 1. 5. A textile treatment composition containing a) from 0.1-40% by weight of at least one polysiloxane polymer as defined in claim 1, b) from 0 to 30% by weight of further silicones, c) from 0 to 30% by weight of cationic and/or nonionic surfactants, d) from 0 to 60% by weight of further ingredients such as further wetting agents, softeners, lubricants, water soluble, film forming and adhesive polymers, scents, dyes, stabilizers, fiber and color protection additives, viscosity modifiers, soil release additives, corrosion control additives, bactericides, preservatives and spraying assistants, and e) from 0 to 99.9% by weight of water, said components a) to e) adding up to 100% by weight.
 6. A solid laundry detergent formulation containing a) from 0.05 to 20% by weight of at least one polysiloxane polymer as defined in claim 1, b) from 0 to 20% by weight of further silicones, c) from 0.1 to 40% by weight of at least one nonionic and/or anionic surfactant, d) from 0 to 50% by weight of inorganic builders, e) from 0 to 10% by weight of organic cobuilders, f) from 0 to 60% by weight of further customary ingredients such as standardizers, enzymes, perfumes, complexing agents, corrosion inhibitors, bleaches, bleach activators, cationic surfactants, bleach catalysts, dye transfer inhibitors, soil antiredeposition agents, soil release polyesters, dyes, bactericides, dissolution improvers and/or disintegrants, said components a) to f) adding up to 100% by weight.
 7. A liquid laundry detergent formulation containing a) from 0.05 to 20% by weight of at least one polysiloxane polymer as defined in claim 1, b) from 0 to 20% by weight of further silicones, c) from 0.1 to 40% by weight of at least one nonionic and/or anionic surfactant, d) from 0 to 20% by weight of inorganic builders, e) from 0 to 10% by weight of an organic cobuilder, f) from 0 to 60% by weight of further customary ingredients such as sodium carbonate, enzymes, perfume, complexing agents, corrosion inhibitors, bleaches, bleach activators, bleach catalysts, cationic surfactants, dye transfer inhibitors, soil antiredeposition agents, soil release polyesters, dyes, bactericides, nonaqueous solvents, solubilizers, hydrotropes, thickeners and/or alkanolamines, g) from 0 to 99.85% by weight of water, said components a) to g) adding up to 100% by weight.
 8. A fabric care rinse composition containing a) from 0.05 to 40% by weight of at least one polysiloxane polymer as defined in claim 1, b) from 0 to 20% by weight of further silicones, c) from 0.1 to 40% by weight of at least one cationic surfactant, d) from 0 to 30% by weight of nonionic surfactants, e) from 0 to 30% by weight of further customary ingredients such as silicones, other lubricants, wetting agents, film forming polymers, scents, dyes, stabilizers, fiber and color protection additives, viscosity modifiers, soil release additives, corrosion control additives, bactericides and preservatives, and f) from 0 to 99.85% by weight of water, said components a) to f) adding up to 100% by weight. 